Nitrogen-containing spiranes and siloxanes and their preparation



United States Patent 3,170,941 NITROGEN-CONTAINING SPIRANES AND SILOXANES AND THEIR PREPARATION John L. Speier, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich, a corporation of Michigan No Drawing. Filed Oct. 12, 1961, Ser. No. 144,538 20 Claims. '(Cl. 260-4481) wherein R is selected from the group consisting of monovalent hydrocarbon, monovalent hydrocarbon radicals containing oxygen in the form of I I -o0o- I I linkages, aminoalkyl, aminophenyl and halogenophenyl radicals and R is a divalent saturated aliphatic hydrocarbon radical, wherein the nitrogen atom is attached to .a carbon atom which is at least the third and not more than the sixth carbon atom away from the silicon atom.

R in the above formula can be a monovalent hydrocarbon radical. Specific examples of such radicals are alkyl radicals, such as methyl, ethyl, t-butyl and octyl; alkenyl radicals, such as vinyl, ally-l and butadienyl; cycloalkyl radicals, such as cyclobutyl, cyclopentyl and cycohexyl; cycloalkenyl radicals, such as cyclopentenyl and cyclohexenyl; aryl radicals such as phenyl and xenyl; aralkyl radicals such as benzyl and xylyl and alkaryl radicals, such as tolyl. R can be a monovalent hydrocarbon radical containing oxygen in the form of Specific examples of such radicals are and CH OC H R can also be an aminoalkyl group, such as aminomethyl, aminoethyl, aminohexyl and aminooctyl. R can also be an aminophenyl radical. R can be a halogenophenyl group, such as p-ClC H and rn-BrC H R is a divalent saturated aliphatic hydrocarbon radical, wherein the nitrogen atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the silicon atom.

Suitable examples of R are CH CH CH CHZ(CH2)2CHZ 2( 2)3 2 and CH (CH CH The R group can also be a branched alkylene group such as -CH CH CH CH CH CH (CH CH CH CH and I: 2CH3] CH2CH2CH2. Thus, there can be more than six carbon atoms in the R group as long as there are no more than six carbon atoms in the chain between the silicon atom and the nitrogen atom.

linkages.

ice

These spirane compounds can be prepared by effecting a reaction between (1) a di-(halogenoalkyl)-dihalogenosilane of the formula (XR') SiX and (2) an amino compound of the formula RNH R and R are as defined above and X is a chlorine, bromine or iodine atom.

The reaction between (1) and (2) takes place within a Wide range of atmospheric and superatmospheric pressures. Superatmospheric pressures are preferred for faster and more complete reaction. The reaction can be carried out at various temperatures. Generally, temperatures ranging from about to C. are advantageously employed. However, the reaction appears to go satisfactorily in many instances at room temperature.

After the reaction has been concluded, the hydrogen halide produced is removed and the resultant product is separated by distillation or other suitable means. The amount of amino compound employed for this reaction should be sufiicient to react with all the halogen atoms in (1). It is usually desirable that the reaction be conducted using an excess of the amino compound since this permits easier separation of the pure product, because the amino compound acts as a hydrogen halide acceptor. If desired, inert hydrogen halide acceptors such as tributylamine, pyridine and quinoline may be substituted in place of some of the excess amino compound intended as a hydrogen halide acceptor. It is preferable to use between 7 and 10 mols of (2) per mol of (1).

The spiranes of this invention can be hydrolyzed and condensed to produce nitrogen-containing polysiloxanes. The siloxanes produced from these spiranes have the unit formula (RNHR') SiO, wherein R and R are as defined above.

The spiranes of this invention can be hydrolyzed with silaues containing hydrolyzable groups to produce copolymers containing (RNHR) SiO units and R1.SiO

units. R' can be a monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon radical, such as -CH CH CF or CH Cl. The subscript n has a value of from 1 to 3 inclusive. The spiranes of this invention can also be cohydrolyzed with nitrogen-containing cyclic silanes of the formula to produce copolymers containing (RNHR) SiO units and units. R and R are as defined above. Z is an alkyl or phenyl radical or an alkyl radical containing oxygen in the form of linkages, such as -CH OCH R is a monovalent hydrocarbon radical and a has a value of from 0 to 2 inclusive. The nitrogen-containing cyclic silanes which are used to produce these copolymers are fully described in applicants copending application entitled Nitrogen-Containing Cyclic Silanes, Their Preparation and Hydrolysis, filed simultaneously herewith, the disclosure of which is hereby incorporated in this application by reference.

The hydroxy endblocked nitrogen-containing siloxanes of this invention can be reacted with the cyclic silanes 3 4 disclosed in applicants copending application (identified EXAMPLE 1 above) to produce a nitrogen-containing siloxane which is endblocked with units containing nitrogen attached to y p pyb 05113116 silicon through a divalent saturated aliphatic hydrocar- 11101) and methylamine gq 111015) Were heatiid at bon radical. These endblocked siloxanes are produced 100 C. for 8 hours. Themass was then cooled and the b ff ti a ti b t layers separated. Distillatlon of the top layer at 30 mm.

pressure gave a 41 percent yield of (1) (RNHR) HO]: SiO b (RNHR) d 10 [CH NCH CH(CH )CHg]Si[CHzCH(CHg)CHzNCHsl an (2) Into a flask containing 9.92 g. (0.05 mol) of the above (RNR)SiRz product there was added 0.9 g. of distilled water. A tern- A d t f th I l perature rise from 27 C. to 140 C. occurred after stirring pro uc 0 6 the reactants. A quantitative yield of siloxane of the unit RI! R1! fOlmLIlEt (RNHR)SiOl: Si sim'Nnm R (RNHR) bR CH is obtained. R, R and R" are as defined above. The (OHENHCHZJJHCHWSiO subscript b has a value of at least 1.

The polymers and copolymers of this invention can be was Obtamed' employed as a basis for rubbers and oils. These poly- EXAMPLE 2 siloxanes are also useful as corrosion inhibitors in solutions I that are in contact with steel. The siloxanes of the unit h following spiranes are bt i d h th f ll i formula R'h can be used as cul'lng agents 111 di-(halogenoalkyl) dihalogenosilanes and amino compo y e ha I I pounds are reacted in accordance with the procedure of The following examples are illustrative only and should Example 1. The following siloxanes are obtained when not be construed as limiting the invention which is properthese spiranes are hyrolyzed in accordance with the proly delineated in the appended claims. cedure of Example 1.

Table I Reactants Spirane Unit formula of siloxane product Silane Amine [C1CH2(CH2) Z HzlzSiClz osHuNH: lcsHnN H2(CH2)2CH2] i[CH2(CH2): [C5H 1NHCH2(CH2)zcHflzsio CH2NC5H11] [BrCHflCBmCHflzSiBn CH zCHCHzNHg... [CH2:CHGH2NCH2(CH2)4CH2]SHCHQ [CHz=CHCH2N11CH (CH2)bH]g0 (CH2)4CH2NCHzCH=CH2] l 2(C 2)3C 2]2 i 2 CsHsNEz .a [CuHaNCH2(CH2)3CH2] i[CH2(CH2)a [CeH5NHCH2(CH2)sCH2]SiO CHZNCGH5] llhlzSiO CH (CHZCHB) CHzNCBzCHzNHz] (ClCH2CH2CH2hSiCl2 NHzCsllgNI-Iz U (NH2C6H4NCH2CH2CH2)51(CHzCEzCHzN (NH2CGH-XNHOH2CH2CHQ2SlO I (C1CH2CH2CHz)gSiCl'2-. D'CICGH4NH2 (ClCoHaN'CHzCHzCHQSi(CHzCH2CH2N (C1GfiH-jNHCH2CH2CH2)2SiO CsH4Cl) (ClCHzCHzCHz)gSiClg CH3OCHgCHgNHz" (CBaOCH CHgNCHgCHQCHZ)SKCH CH (C1130 CH2CHzI IHCH2CH2CHz)zSiO CH NOH2CHZO CH3) 3,170,941 5 r 6 EXAMPLE 3 valent hydrocarbon, monovaient hydrocarbon radicals Copolymers containing siloxane units of the following contammg Oxygen m the form of formulae are obtained when the following silanes and spiranes are hydrolyzed in accordance with the procedure shown in Example 1.

Table II Reactants v Siioxane Units Contained in Copolymer Siiane Spirane 50 mol'percent of (CH3)2Si(O CHah--- 50 moi percent of [CH 1!ICH2CH(CHa) CHz]Si[CHz (CHahSiO and [CHaNHCH2CH(OH3) CHghSiO CH(CH3) CHgNCHal moi percent oi (CGHQSKOCHQLM- 75 moi percent of [NH2CH2 (C 11 SiOns and [NH2CH2OH2NH(CH2)5]2SiO 51 moi percent of (CH3) (C1=CH) mol percent of [CaH5N(CH2)4]Si[(OH2)4NC@H5] (0H (CHFCH) SiO and [CeH5NH(CH2)4]gSiO OCH3)2 5 11101 percent Of (C3117) sSi(O 01-13)-. 95 H101 percent 0! [NH2C H4N(CH2) 3]Si[(CH2)31ITCa (C3117) aSiO.5 and [NH2CBH4NH(CH2) alzSiO HiNHz] 50 moi percent of (CFfiOHQCHZ) 50 moi percent of [OH3CHzNCH2CH(CHa)] (CFQCHgCHE) (CH3)SiO and (CH3)Si(O CHs')2 [CH3CH2NHCH2OH(CHa) CHzlzSiO 95 mol percent of [CHzNCHgCHtCHQ CHflSilCHz [CH3NHCH2CE(OH3) CH2](CHa)zSlO.5 and 5 moi percent of [CHaNHCHzCH(CHz)CH2]2SlO [CHaNCHgGH-(CHa) CH2lSi(CHa)2 CH(OH3) CH NCHa] 25 moi percent of 75 moi percent of (CH3) (CH3NHCH2CHzCH2)SiO and I [CHSNHCHzCHzCHflgSiO [CHaNCHgCHzCHflSl v [CH3NCH2CH2CH2]Si[CH2CH2CHzNCHfi] (OH3)(OCH3) EXAMPLE 4 linkages, aminoalkyl, aminophenyl and halogenophenyl The following siioxanesvare obtained when the follow- 5 radicals is divalenf Saturated ElliPhatic y ing li il are t d i h h foll i hydroxy carbon radical wherein the nitrogen atom is attached to a endblocked nitrogen-containing siloxanes. This reaction carbon atom Whlch 15 at least the t lrd and not more than is etfected merely by adding the cyclic silanes to the the Sixth carbon atom y m the l n at msiloxane at a ratio of 2 mois of the cyclic siiane per 1 50 The p ane of claim 1, wherein R is a monovalent ol f iloxm hydrocarbonradical and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is the third carbon atom away from the silicon atom.

3. A spirane of the formula That which is claimed is:

1. A spirane of the general formula wherein R is selected from the group consisting of mono- 4. A spirane of the general formula CHgNCHgCHgCHzSiCHgCHzCHgNCHs.

CH5NCH2CHgCHg iCHgCH CHgNCaHs.

7. A method for making a spirane of the formula which comprises effecting a reaction between ')2 2 and (2) RNH wherein R is selected from the group consisting of monovalent hydrocarbon, monovalent hydrocarbon radicals containing oxygen in the form of linkages, aminoalkyl, aminophenyl and halogenophenyl radicals, R is a divalent saturated aliphatic hydrocarbon radical wherein the silicon atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the other substituent attached to R and X is a halogen atom selected from the group consisting of chlorine, bromine and iodine.

8. The method of claim 7, wherein R is a monovalent hydrocarbon radical, R is a divalent saturated aliphatic hydrocarbon radical wherein the silicon atom is attached to a carbon atom which is the third carbon atom away from the other substituent attached to R and X is chlorine.

9. The method for making the spirane of claim 3 which comprises effecting a reaction between (1) [CICH CH (CH CH SiCl and CH NH 10. A method for making a polysiloxane of the unit formula (RNHR) SiO which comprises hydrolyzing and condensing a spirane of the general formula wherein R is selected from the group consisting of monovalent hydrocarbon, monovalent hydrocarbon radicals containing oxygen in the form of I I --COC I I V linkages, aminoalkyl, aminophenyl and halogenophenyl radicals and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the silicon atom.

11. The method of claim 10, wherein R is a monovalent hydrocarbon radical and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is the third carbon atom away from the silicon atom.

12. The method of claim 10, wherein R is an alkyl radical of from 1 to 6 inclusive carbon atoms and R is 13. A polysiloxane of the unit formula (RNHR) SiO, wherein R is selected from the group consisting of monovalent hydrocarbon, monovalent hydrocarbon radicals containing oxygen in the form of io l I I linkages, aminoalkyl, aminophenyl and halogenophenyl radicals and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the silicon atom.

14. The polysiloxane of claim 13, wherein R is a monovalent hydrocarbon radical and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen is attached to a carbon atom which is the third carbon atom away from the silicon atom.

15. The polysiloxane of claim 13, wherein R is an alkyl radical of from 1 to 6 inclusive carbon atoms and R is 16. A copolymeric siloxane composed of (1) units of the formula (RNHR'hSiO, wherein R is selected from the group consisting of monovalent hydrocarbon, monovalent hydrocarbon radicals containing oxygen in the form of I I linkages, aminoalkyl, aminophenyl and halogenophenyl radicals and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the silicon atom and (2) units selected from the group consisting of (a) units of the formula wherein R is selected from the group consisting of monovalent hydrocarbon and halogenated monovalent hydrocarbon radicals and n has an average value of from 1 to 3 inclusive and (b) units of the formula (RNHR')SlOj wherein R, R are as defined above, R is selected from the group consisting of monovalent hydrocarbon radicals and monovalent hydrocarbon radicals containing oxygen in the form of I I linkages and a has a value of from O to 2 inclusive. 17. A copolymeric siloxane composed of (1) units of the formula (RNHR) SiO, wherein R is a monovalent hydrocarbon radical and R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is the third carbon atom away from the silicon atom and (2) units of the formula n nsiot l wherein R is a monovalent hydrocarbon radical and n has an average value of from 1 to 3 inclusive.

18. The copolymeric siloxane of claim 17, wherein R and R are alkyl radicals of from 1 to 6 inclusive carbon atoms and R is CH CH(CH )CH 19. A siloxane of the general formula If If (RNHR)S|iOl: SiO :I Si(RNHR) R (RNHR) 11R" wherein R is selected from the group consisting of monovalent hydrocarbon, monovalent hydrocarbon radicals containing oxygen in the form of ';0- l I linkages, arninoalkyl, aminophenyl and halogenophenyl radicals, R is a divalent saturated aliphatic hydrocarbon radical wherein the nitrogen atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the silicon atom, R

is a monovalent hydrocarbon radical and b has a value of at least 1.

References Cited by the Exam'mer UNITED STATES PATENTS 2,738,357 3/56 Speier 260-465 2,921,950 1/60 JcX et a1. 26046.5 2,947,771 8/60 Bailey 260448.2

FOREIGN PATENTS 642,823 6/62 Canada.

WILLIAM H. SHORT, Primary Examiner.

M. STEARMAN, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,170,941 February 23, 1965 John L. Speier It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 54 to 56, the formula should appear as shown below instead of as in the patent:

(RNHR)SiO columns 3 and 4, Table I, fourth column, line 3 thereof, for n H [C H NHCH (CH CH ]S1O read [C H NHCH (CH CH S1O columns 5 and 6, Table II, third column line 2 thereof, for

(c H )sio and [NH CH CH NH(CH SiO Signed and sealed this 28th day of September 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,170,941 February 23, 1965 John L. Speier It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 54 to 56, the formula should appear as shown below instead of as in the patent:

columns 3 and 4, Table I, fourth column, line 3 thereof, for

columns 5 and 6, Table II, third column, line 2 thereof, for

Signed and sealed this 28th day of September'1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A SPIRANE OF THE GENERAL FORMULA
 7. A METHOD FOR MAKING A SPIRANE OF THE FORMULA
 10. A METHOD FOR MAKING A POLYSILOXANE OF THE UNIT FORMULA (RNHR'')2SIO WHICH COMPRISES HYDROLYZING AND CONDENSING A SPIRANE OF THE GENERAL FORMULA 